Aqueous zeolite-containing liquid detergent stabilized with an electrolyte mixture

ABSTRACT

A phosphate-free liquid detergent containing anionic and nonionic surfactants, zeolite, and electrolyte system selected from carbonates, sulfates, chlorides, acetates and citrates with the proviso that the electrolyte system contain at least one carbonate and one sulfate, and water.

This invention relates to a phosphate-free, water-based liquid detergentcontaining zeolite as builder and to a process for its production.

DISCUSSION OF THE RELATED ART

Liquid detergents containing builders are known in large numbers. Inthese water-based concentrates, even basically water-soluble builders,such as sodium tripolyphosphate for example, are partly undissolved andare present in the form of fine particles. In the interests of safety inuse, liquid detergents of the type in question have to be formulated asstabilized homogeneous suspensions. If the tripolyphosphate is replacedby zeolite NaA, the problem of suspension stabilization also has to besolved for this insoluble and fine-particle component. To this end, itis proposed in German patent application 36 05 978 to suspend thezeolite particles in a non-aqueous liquid (liquid nonionic surfactant)and to increase the stability of the suspension by addition of thealuminium salt of a higher aliphatic carboxylic acid (aluminiumtristearate). German patent application 36 25 189 describes non-aqueous,liquid universal detergents containing 25 to 45% by weight of one ormore liquid nonionic surfactants, 10 to 20% by weight salts ofnitrilotriacetic acid, 10 to 25% by weight zeolite and an anti-gellingagent, for example a nonionic surfactant reacted with succinic anhydrideor an alkylene glycol monoalkyl ether, and aluminium tristearate asstabilizer.

U.S. Pat. No. 4,018,720 describes water-based liquid detergentscontaining 7 to 25% by weight of a mixture of alkyl sulfates or alkylether sulfates and alkyl benzenesulfonates, 6 to 25% by weight of aphosphate builder, 3 to 20% by weight of an alkali metal sulfate asstabilizer and, optionally, 1 to 10% by weight of an aluminosilicate ascobuilder. The sole use of alkyl zinc sulfonate as anionic surfactantleads to physically unstable compositions in the same way as theaddition of solvents, such as alcohols or glycols.

Canadian patent application 1,202,857 describes stable, water-basedliquid detergents containing 13 to 38% by weight zeolite, 5 to 40% byweight unsaturated C₁₆₋₂₂ fatty acid soap, 7 to 20% by weightsurfactants, such as alkoxylated nonionic surfactants and amine oxides,5 to 15% by weight water-soluble builders, such as polycarboxylates andpyrophosphate, and 30 to 70% by weight water. The detergents in questionmay also contain amphoteric and other anionic surfactants, includingsaturated soaps.

European patent application 75 976 describes alkaline water-based liquiddetergents which contain 7 to 30% by weight zeolite, 5 to 40% by weightof an unsaturated C₁₆₋₂₂ fatty acid soap, 1 to 30% by weight of anonionic surfactant, 5 to 15% by weight of a water-solublepolycarboxylate and 20 to 82% by weight water, but which are free fromsynthetic anionic surfactants because they would destabilize the perfumeesters present in this stable liquid mixture.

European patent application 86 614 describes water-based liquiddetergents containing anionic and/or nonionic, cationic and amphotericsurfactants, water-insoluble, suspended and optionally water-solublebuilders and other electrolytes; sodium sulfate must not be present inquantities above 3% by weight. In the interests of stability,tripolyphosphate or mixtures of tripolyphosphate and other buildersubstances is/are preferably used as builder. Whereasphosphate-containing suspensions showed no signs of sedimentation, insome cases even after storage for 12 months at room temperature,phosphate-free detergents containing 13.4% by weight zeolite and 8.9% byweight silicate or 13.6% by weight zeolite and 9.0% by weight silicateas builders were stable in storage for only month at room temperature.

European patent application 142 185 describes stable water-based liquiddetergents containing condensed phosphates and/or nitrilotriacetatetogether with zeolite NaY. The suspensions have a pH value of 7 to 9.The detergents contain 1 to 60% by weight surfactants, 0.5 to 30% byweight phosphate and/or nitrilotriacetate and 1 to 45% by weightzeolite. The surfactants may consist of anionic and nonionic surfactantswhich are preferably used in a ratio of 10:1 to 1:10. Zeolite NaA wasfound to be unsuitable for use in these detergents, distinct phaseseparation occurring after storage for only 15 days at room temperature.

European patent application 151 884 describes water-based liquiddetergents containing builders, preferably phosphates, and surfactantsin a ratio of at least 1.5:1 and also electrolytes. The quantity ofelectrolyte required to stabilize a certain predetermined suspension ofwater, surfactants and builders is determined by conductivitymeasurements. Where electrolyte salts are continuously added, theelectrical conductivity passes through a first minimum in which thesuspension is stable.

European patent application 170 091 also describes water-based liquiddetergents containing surfactants, electrolytes - which includewater-soluble builders, but which contain less than 3% by weight sodiumsulfate - and suspended builders. In this case, too, tripolyphosphate ispreferably used as the builder for the same reasons of stability as inEuropean patent applications 86 614 and 151 884. The detergents can beseparated into at least two phases, of which at least one is an aqueousphase, by centrifugation for 17 hours/25° C. at 800 times the earth'sattraction. Stable detergents contain such quantities of dissolvedelectrolyte that 2 to 4.5 gram ions alkali metal ion per liter arepresent in the aqueous phase.

According to the teaching of European patent application 295 021,water-based, non-sedimenting, liquid crystalline surfactantconcentrates, which can be transported and stored with no loss ofstability, contain 25 to 80% by weight surfactants and up to 10% byweight, based on the quantity of surfactant, of electrolytes. However,sodium sulfate is only present in traces, if at all and - in the formercase--is introduced into the concentrates as an impurity in the anionicsurfactants. The concentrates may be rapidly diluted or made up intoliquid detergents by addition of other detergent constituents, forexample by addition of suspendable builders, preferablytripolyphosphate, and optionally electrolytes. The use of electrolyteswith no builder properties is less preferred.

European patent application 301 882 describes a liquid detergent whichmay contain builders, such as phosphates and zeolite, and which containsviscosity-reducing (co)-polymers, for example polyethylene glycol,polyacrylates, polymaleates, polysaccharides and sulfonatedpolysaccharides. The polymers are only partly dissolved in the aqueousphase, the remainder being part of a phase dispersed in the aqueousphase. The detergents are regarded as sufficiently stable if no morethan 2% phase separation occurs during storage for 21 days at 25° C.

The problem addressed by the present invention was to provide aphosphate-free, water-based zeolite-containing liquid detergent which isstable in storage for at least 3 months both at room temperature and at40° C., does not have any tendency towards sedimentation, even duringtransport at temperatures of 5° to 60° C., and satisfies the performancerequirements of modern liquid detergents.

DESCRIPTION OF THE INVENTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients or reaction conditions usedherein are to be understood as modified in all instances by the term"about".

Accordingly, the present invention relates to a phosphate-freezeolite-containing liquid detergent which contains 10 to 30% by weightanionic and nonionic surfactants, 10 to 25% by weight zeolite, 1 to 10%by weight of an electrolyte system consisting of at least twoelectrolytes from the group consisting of carbonates, sulfates,chlorides, acetates and citrates, and 40 to 60% by weight water, theelectrolyte system consisting of at least one carbonate and one sulfate.

The detergents according to the invention preferably contain 5 to 20% byweight typical anionic surfactants from the class of sulfonates andsulfates. Preferred surfactants of the sulfonate type are C₉₋₁₃ alkylbenzenesulfonates, more particularly C₁₂ alkyl benzenesulfonate, andsulfonates based on oleochemicals, such as the esters of α-sulfonatedfatty acids (ester sulfonates), for example the α-sulfonated methylesters of hydrogenated coconut oil, palm kernel oil and tallow fattyacids. Suitable surfactants of the sulfate type are, for example, thesulfuric acid monoesters of primary alcohols of natural and syntheticorigin, i.e. fatty alcohols such as, for example, coconut oil fattyalcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl,palmityl or stearyl alcohol, or C₁₀₋₂₀ oxoalcohols, and sulfuric acidmonoesters of secondary alcohols having the same chain length, thesulfuric acid monoesters of primary alcohols based on oleochemicalsbeing preferred. Sulfuric acid monoesters of alcohols ethoxylated with 1to 6 mol ethylene oxide, such as linear C₁₂₋₁₈ fatty alcohols or2-methyl-branched C₉₋₁₁ alcohols containing on average 3.5 mol ethyleneoxide, are also suitable. Sulfated fatty acid monoglycerides may also beused. The sulfates and sulfonates may be present individually or inadmixture. Preferred detergents contain 5 to 17% by weight and, moreparticularly, 8 to 16% by weight C₉₋₁₃ alkyl benzenesulfonates or 10 to20% by weight of a mixture of C₉₋₁₃ alkyl benzenesulfonates with one ormore other sulfonates and/or sulfates in any mixing ratio.

Other suitable anionic surfactants are soaps, preferably saturated fattyacid soaps, such as the salts of lauric acid, myristic acid, palmiticacid and stearic acid. Soap mixtures derived from natural fatty acids,for example coconut oil, palm kernel oil or tallow fatty acids, areparticularly suitable. Soaps of which 50 to 100% by weight consist ofsaturated C₁₂₋₁₈ fatty acid soaps and 0 to 50% by weight of oleic acidsoap are also suitable. The detergents according to the invention maycontain 0 to 5% by weight soaps. Preferred detergents have a soapcontent of 1 to 3.5% by weight.

The anionic surfactants may be present in the form of their sodium,potassium or ammonium salts and also in the form of soluble salts oforganic bases, such as mono-, di-or triethanolamine.

In addition, the detergents according to the invention preferablycontain 5 to 10% by weight nonionic surfactants. Suitable nonionicsurfactants are, for example, typical ethoxylated fatty alcohols, moreparticularly adducts of 2 to 7 mol ethylene oxide (EO) with linearprimary alcohols, for example with coconut oil, tallow fatty or oleylalcohol, or with 2-methyl-branched primary alcohols (oxoalcohols). Moreparticularly, C₁₂₋₁₄ alcohols containing 3 EO or 4 EO, C₁₃₋₁₅ alcoholscontaining 3, 5 or 7 EO, C₁₂₋₁₈ alcohols containing 3, 5 or 7 EO andmixtures thereof, such as mixtures of C₁₂₋₁₄ alcohol containing 3 EO andC₁₂₋₁₈ alcohols containing 5 EO, are used in quantities of 5 to 9% byweight.

The detergents according to the invention contain zeolite NaA asbuilder. Other suitable builders are mixtures of zeolite NaA and NaX,the percentage content of the zeolite NaX in such mixtures best beingbelow 30% and, more particularly, below 20%. Suitable zeolites containno particles larger than 30 μm in size, at least 80% consisting ofparticles smaller than 10 μm in size. Their average particle size(volume distribution, as measured with a Coulter Counter) is in therange from 1 to 10 μm. Preferred zeolites have an average particle sizeof 2 to 4 μm. Their calcium binding power, as determined in accordancewith German patent application 24 12 837, is in the range from 100 to200 mg CaO/g. The zeolites, of which 10 to 25% by weight are present inthe detergents according to the invention, may still contain excessalkali from their production. The zeolite content of the detergentsaccording to the invention is preferably 12 to 20% by weight and, morepreferably, 14 to 19% by weight. The ratio of surfactants to zeolite ispreferably 0.8:1 to 1.4:1 and, more preferably, 1:1 to 1.4:1.

The suspensions according to the invention of water, surfactants andzeolite are stabilized by an electrolyte system which consists of atleast two salts, preferably sodium salts and/or triethanolammoniumsalts, from the group consisting of carbonates, chlorides, sulfates,acetates and citrates, although it consists of at least one carbonateand one sulfate. The percentage content of the electrolyte system in thedetergent as a whole is 1 to 10% by weight. 0.5 to 4% by weight andpreferably 0.5 to 2% by weight of the electrolyte system consists ofcarbonate, 0.5 to 8% by weight and preferably 1 to 6% by weight ofsulfate, 0 to 4% by weight and preferably o.1 to 2% by weight ofchloride, 0 to 4% by weight and preferably 0.1 to 2.5% by weight ofacetate and 0 to 1.5% by weight and preferably 0.1 to 1% by weight ofcitrate which is introduced into the suspension in the form of citricacid and which is formed by reaction with excess alkali. Preferredelectrolyte systems consist of 3 or 4 different electrolytes, moreparticularly (based on the detergent as a whole) of 0.5 to 2% by weightsodium carbonate, 4 to 6% by weight sodium sulfate and 0.8 to 1.5% byweight citrate, for example sodium citrate or triethanolammoniumcitrate, or of 0.5 to 1.5% by weight sodium carbonate, 3.5 to 5.5% byweight sodium sulfate and 1.0 to 2.0% by weight sodium chloride or of0.5 to 1% by weight sodium carbonate, 4 to 6% by weight sodium sulfateand 0.5 to 4% by weight sodium acetate or of 0.5 to 1% by weight sodiumcarbonate, 3 to 5.5% by weight sodium sulfate, 0.5 to 1.5% by weightsodium chloride and 0.5 to 2.5% by weight sodium acetate. The ratio ofzeolite to the electrolyte system is preferably 10:3 to 10:6 and, morepreferably, 10:4 to 10:5.

The detergents according to the invention contain 40 to 60% by weightand preferably 42 to 55% by weight water.

The pH value of the detergents is in the range from 8 to 12, preferablyin the range from 8.5 to 10.5 and, more preferably, in the range from 9to 10. The density of the detergents is from 1.1 to 1.25 g/ml andpreferably from 1.15 to 1.22 g/ml. The detergents according to theinvention have a yield point of at least 3 Pa. Preferred detergents haveyield points of 4 to 35 Pa. Their viscosity (Brookfield viscosimeter,spindle No. 6, 10 r.p.m.) is in the range from 2,000 to 11,000 mPas,preferably in the range from 3,000 to 9,000 mPas and, more preferably,in the range from 3,500 to 8,500 mPas. The stability of the detergentsin storage was tested over a period of 7 months both at room temperatureand at 40° C. The detergents were stable in storage for at least 3months. Some detergents stored for even longer periods showed no signsof sedimentation after 4 months and even after as long as 7 months. Thedetergents can be transported at temperatures of 5° to 60° C.

The foaming power of the surfactants can be reduced by the addition of0.05 to 2% by weight non-surface-active organic substances. Suitablefoam inhibitors are, for example, known polysiloxane/silica mixtures inwhich the fine-particle silica is preferably silanized. Thepolysiloxanes may consist both of linear compounds (silicone oils) andof crosslined polysiloxane resins and mixtures thereof. Other suitablefoam inhibitors are paraffin oils, microparaffins and paraffin waxes.Mixtures of various foam inhibitors, for example mixtures of siliconeoil and paraffin oil, may also be used with advantage. It isparticularly preferred to use 0.1% by weight, based on the detergent asa whole, of silicone oil.

The detergents preferably contain 0.5 to 5% by weight alcoholscontaining 2 to 3 carbon atoms and 1 to 3 hydroxyl groups, such asethanol, propanol, propylene glycol and glycerol. Propylene glycol andglycerol, either on their own or in admixture with ethanol, arepreferably used in quantities of 2 to 3.5% by weight.

The detergents may also contain small quantities of free base, such astriethanolamine or sodium hydroxide, to keep the pH value in the rangefrom 9 to 12.

In addition to the ingredients mentioned, the detergents may optionallycontain other known additives of the type typically used in detergents,for example salts of polyphosphonic acids, optical brighteners, enzymes,bleaches stable in water-based detergents, hydrotropes and dyes andfragrances, in the usual quantities which do not affect the stability ofthe suspensions according to the invention.

The neutrally reacting sodium salts of, for example,1-hydroxyethane-1,1-diphosphonate and diethylene triamine pentamethylenephosphonate are preferably used in quantities 0.1 to 1.5% by weight asthe polyphosphonic acid salts. The total phosphorus content of thedetergents as a whole is preferably less than 0.5%.

The detergents may contain derivatives of diaminostilbene disulfonicacid or alkali metal salts thereof as optical brighteners. Suitableoptical brighteners are, for example, salts of4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazin-6-ylamino)-stilbene-2,2'-disulfonicacid or compounds of similar structure which, instead of the morpholinogroup, contain a diethanolamino group, a methylamino group, an anilinogroup or a 2-methoxyethylamino group. Brighteners of the substituted4,4'-distyryl diphenyl type, for example the compound4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl, may also be present.Mixtures of the brighteners mentioned above may also be used. Themaximum content of brighteners in the detergents according to theinvention is 0.5% by weight, quantities of 0.02 to 0.1% by weightpreferably being used.

Suitable enzymes are those from the class of proteases, lipases,amylases or mixtures thereof. Their percentage content in the detergentsmay be from 0.2 to 1% by weight.

In one preferred embodiment, the detergents contain 8 to 16% by weightC₉₋₁₃ alkyl benzenesulfonate, more particularly C₁₂ alkylbenzenesulfonate, 1 to 3.0% by weight saturated C₁₂₋₁₈ fatty acid soapin the form of the sodium and/or triethanolammonium salts, 5 to 9% byweight nonionic surfactants, 14 to 19% by weight zeolite containingbound water, 0.5 to 1.5% by weight sodium carbonate, 3 to 6% by weightsodium sulfate, 0 to 1.5% by weight 1-hydroxyethane-1,1-diphosphonateand/or diethylenetriamine pentamethylene phosphonate, 0.1% by weightsilicone oil and 43 to 54% by weight water.

In another preferred embodiment, the detergents contain surfactants,zeolite, phosphonate, silicone oil and water as above and also 0.5 to 1%by weight sodium carbonate, 4 to 6% by weight sodium sulfate, 1.5 to 2%by weight sodium acetate and 2 to 3% by weight glycerol or propyleneglycol.

It is also preferred to use detergents containing surfactants, zeolite,phosphonate, silicone oil, sodium carbonate, sodium sulfate and water asabove and also 0.8 to 1.5% by weight citrate, for example sodium citrateand/or triethanolammonium citrate, and 2 to 3% by weight glycerol or amixture of 2/3rds glycerol and 1/3rd ethanol.

The invention also relates to a process for the production of the liquiddetergents described above. The liquid detergents may be produced inknown manner. To this end, 35 to 60% and preferably 40 to 58% water,based on the total quantity of water to be present in the detergent, andthe foam inhibitor are preferably introduced into a reactor equippedwith a stirrer system. The other components are added in such a way thatlarge numbers of air bubbles are not stirred in. Where soap is to formpart of the detergent, the corresponding fatty acid or the correspondingfatty acid mixture is heated to 60° to 80° C. and is stirred into thewater introduced beforehand which has also been heated to 60° to 80° C.in this particular case. Thereafter, the fatty acid is best neutralizedwith triethanolamine and/or sodium hydroxide preferably added in theform of an aqueous solution. Zeolite NaA may be added both in the formof a powder and in the form of an aqueous suspension, the addition of a40 to 55% by weight aqueous zeolite suspension being preferred. Theelectrolyte salts, carbonate and sulfonate and optionally chloride andacetate, may also be introduced in powder form or in the form of anaqueous solution.

EXAMPLES EXAMPLE 1

This Example describes the production of a liquid detergent (D1)according to the invention in a 900 kg batch.

195.25 kg water and 0.9 kg silicone oil (silicone foam inhibitor VP1132, a product of Wacker-Chemie GmbH) were introduced into an 800 ltank reactor. After the mixture of water and silicone oil had beenheated to 70° C., 16.00 kg C₁₂ fatty acid (94%), which had also beenheated to 70° C., were introduced.

The following components in the quantities indicated were added asfurther constituents:

150.00 kg of a 55% by weight aqueous solution of sodium dodecylbenzenesulfonate,

60.00 kg C₁₃₋₁₅ alcohol containing 7 ethylene oxide groups (EO),

305.00 kg of a 52% by weight aqueous zeolite suspension stabilized withtallow fatty alcohol containing 5 EO,

100.00 kg of a 50% by weight aqueous sodium sulfate solution,

10.00 kg of a 50% by weight aqueous sodium carbonate solution,

7.20 kg citric acid,

12.20 kg triethanolamine,

25.00 kg glycerol and 4.5 kg perfume, 0.45 kg optical brightener, 4.50kg protease and 9.00 kg 1-hydroxyethane-1,1-diphosphonate disodium salt.

After mixing, the mixture was stirred for 20 minutes. The suspensionobtained was degassed in vacuo (120 mm Hg column) to remove the airintroduced during the dispersion process.

Density: 1.2 g/ml

pH value: 9.20

Viscosity (Brookfield viscosimeter, spindle No. 6, 10 r.p.m.): 4,000mPas

Yield point: 4.2 Pa

Stability in storage: The storage time was 7 months. In both cases, nosedimentation occurred over this period at storage temperatures of 40°C. and room temperature.

EXAMPLE 2

Further detergents D2 - D5 according to the invention were produced asin Example 1.

D2 contained 9.5% by weight dodecyl benzenesulfonate, 1.7% by weight C₁₂fatty acid, 6% by weight C₁₃₋₁₅ alcohol containing 7 EO, 3% by weightC₁₂₋₁₄ alcohol containing 3 EO, 1.3% by weight triethanolamine, 17% byweight zeolite NaA, 2.0% by weight sodium carbonate, 4.0% by weightsodium sulfate, 1.0% by weight citric acid, 3% by weight glycerol and52.05% by weight water. The storage time was 5 months. No sedimentationoccurred over this period either at 40° C. or at room temperature.

D3 contained 14% by weight dodecyl benzenesulfonate, 8% by weight C₁₂₋₁₄alcohol containing 5 EO, 0.5% by weight sodium hydroxide, 18% by weightzeolite NaA, 0.5% by weight sodium carbonate, 5.0% by weight sodiumsulfate, 2.0% by weight sodium chloride, 2% by weight glycerol, 1% byweight ethanol and 47% by weight water. The storage time was 4 months.No sedimentation occurred over this period either at 40° C. or at roomtemperature.

D4 contained 10% by weight dodecyl benzenesulfonate, 1.8% by weightC₁₂₋₁₄ fatty acid, 1.4% by weight triethanolamine, 6% by weight of amixture of C₁₂₋₁₈ alcohol containing 5 EO and C₁₂₋₁₄ alcohol containing3 EO, 17% by weight zeolite NaA, 0.5% by weight sodium carbonate, 5.5%by weight sodium sulfate, 2.0% by weight sodium acetate, 3% by weightpropylene glycol and 50.1% by weight water. The storage time was 5months. No sedimentation occurred over this period either at 40° C. orat room temperature.

D5 was produced from 9.8% by weight dodecyl benzenesulfonate, 8.0% byweight C₁₂₋₁₄ alcohol containing 5 EO, 4.9% by weight C₁₂ fatty acid,1.1% by weight sodium hydroxide, 17.5% by weight zeolite NaA, 2% byweight glycerol, 1% by weight ethanol, 0.5% by weight sodium carbonate,6.0% by weight sodium sulfate, 0.9% by weight citric acid, 0.5% byweight protease, 0.1% by weight silicone oil and 47.7% by weight water.The storage time was 61/2 months. No sedimentation occurred over thisperiod either at 40° C. or at room temperature.

EXAMPLE 3

This Example describes the performance testing of detergent D1 accordingto the invention which was carried out under the following conditions ina domestic washing machine with a horizontally arranged drum (type MieleW 433):

Washing temperature: 60° C.

One-wash cylce--coloreds program

Water hardness: 16°d (d=German hardness, 160 mg CaO per liter)

Detergent dosage: 224 g

Fabric samples: two test strips with the same soils and 3.5 kg normallysoiled domestic washing

Fourfold determination.

The washing results were optically evaluated (Table 1) using a Zeissreflectometer at 460 nm (blanking out of the brightener effect).Remission differences of 2% and more can be directly noticed by theuser.

    ______________________________________                                        Soil types:                                                                   ______________________________________                                        I     dust/sebum on cotton                                                    II    dust/sebum on crease-resistant cotton                                   III   dust/sebum on polyester/crease-resistant cotton blend                         (50:50)                                                                 IV    dust/sebum on polyester                                                 V     mineral oil on cotton                                                   VI    tea on cotton                                                           VII   red wine on cotton                                                      VIII  cosmetics on crease-resistant cotton                                    ______________________________________                                    

                  TABLE 1                                                         ______________________________________                                        % Remission for                                                               soil             Initial value                                                                            D1                                                ______________________________________                                        I                30.9       64.5                                              II               27.7       69.7                                              III              22.8       44.8                                              IV               30.4       71.7                                              V                17.4       74.6                                              VI               28.1       48.2                                              VII              28.7       55.4                                              VIII             22.4       65.7                                              ______________________________________                                    

The results are comparable with or better than those obtainable withcommercially available products.

We claim:
 1. A phosphate-free liquid detergent composition which isstable toward sedimentation at room temperature for at least 3 monthsconsisting essentially of from about 10 to about 30% by weight ofanionic and nonionic surfactants, from about 10 to about 25% by weightof zeolite, from about 0.5 to about 2% by weight of sodium carbonate,from about 4 to about 6% by weight of sodium sulfate, and from about 0.8to about 1.5% by weight of citrate, and from about 40 to about 60% byweight of water, all weights being based on the weight of said detergentcomposition.
 2. A phosphate-free liquid detergent composition which isstable toward sedimentation at room temperature for at least 3 monthsconsisting essentially of from about 10 to about 30% by weight ofanionic and nonionic surfactants, from about 10 to about 25% by weightof zeolite, from about 0.5 to about 1% by weight of sodium carbonate,from about 3 to about 5.5% by weight of sodium sulfate, from about 0.5to about 1.5% by weight of sodium chloride, and from about 0.5 to about2.5% by weight of sodium acetate, and from about 40 to about 60% byweight of water, all weights being based on the weight of said detergentcomposition.
 3. A detergent composition as in claim 1 wherein saidanionic surfactants are selected from the group consisting of C₉ -C₁₃alkyl benzenesulfonates, alcohol sulfates and ether sulfates, and arepresent in an amount of from about 5 to about 17% by weight of saiddetergent composition.
 4. A detergent composition as in claim 1 whereinsaid anionic surfactants are selected from the group consisting ofsodium and triethanolammonium saturated fatty acid soaps, and arepresent in an amount of from about 1 to about 3.5% by weight of saiddetergent composition.
 5. A detergent composition as in claim 1 whereinsaid zeolite and said electrolyte system are present in a weight ratioof from about 10:3 to about 10:6, respectively.
 6. A detergentcomposition as in claim 1 containing from about 5 to about 10% by weightof said nonionic surfactants.
 7. A detergent composition as in claim 1containing from about 0.5 to about 5% by weight of an alcohol selectedfrom the group consisting of ethanol, propanol, propylene glycol, andglycerol.
 8. A detergent composition as in claim 1 having a pH of fromabout 8 to about 12, and a yield point of at least about 3 Pa.
 9. Adetergent composition as in claim 1 wherein said surfactants and saidzeolite are present in a weight ratio of from about 0.8:1 to about1.4:1, respectively.
 10. A detergent composition as in claim 2 whereinsaid anionic surfactants are selected from the group consisting of C₉-C₁₃ alkyl benzenesulfonates, alcohol sulfates and ether sulfates, andare present in an amount of from about 5 to about 17% by weight of saiddetergent composition.
 11. A detergent composition as in claim 2 whereinsaid anionic surfactants are selected from the group consisting ofsodium and triethanolammonium saturated fatty acid soaps, and arepresent in an amount of from about 1 to about 3.5% by weight of saiddetergent composition.
 12. A detergent composition as in claim 2 whereinsaid zeolite and said electrolyte system are present in a weight ratioof from about 10:3 to about 10:6, respectively.
 13. A detergentcomposition as in claim 2 containing from about 5 to about 10% by weightof said nonionic surfactants.
 14. A detergent composition as in claim 2containing from about 0.5 to about 5% by weight of an alcohol selectedfrom the group consisting of ethanol, propanol, propylene glycol, andglycerol.
 15. A detergent composition as in claim 2 having a pH of fromabout 8 to about 12, and a yield point of at least about 3 Pa.
 16. Adetergent composition as in claim 2 wherein said surfactants and saidzeolite are present in a weight ratio of from about 0.8:1 to about1.4:1, respectively.